The crystal structure of pyrostilpnite from the Plaka mine, Lavrion Mining District, Greece, was refined in the space group P21/c to a final R1 index of 0.0283 on the basis of 2047 reflections with Fo > 4σ(Fo) and 65 refined parameters. Unit-cell parameters of the crystal examined are a = 6.8629(6), b = 15.8800(14), c = 6.2711(5) Å, β = 117.087(2)°, V = 608.48(9) Å3 and Z = 4. Chemical data agree with the stoichiometric formula Ag3SbS3. The crystal structure reported previously was confirmed, although a higher precision of refinement was achieved. It can be described as formed by {010} slabs running along c and connected along a through relatively longer Ag–S bonds. The analysis of the atomic displacement parameters together with a refinement with higher order tensors in the expression of the structure factors revealed no hint for pyrostilpnite as an ionic conductor. A historical background of the ‘ruby silvers’ is also reported.
